CN101535560A - Aqueous formulations and use thereof - Google Patents

Aqueous formulations and use thereof Download PDF

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Publication number
CN101535560A
CN101535560A CNA2007800426981A CN200780042698A CN101535560A CN 101535560 A CN101535560 A CN 101535560A CN A2007800426981 A CNA2007800426981 A CN A2007800426981A CN 200780042698 A CN200780042698 A CN 200780042698A CN 101535560 A CN101535560 A CN 101535560A
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aqueous formulation
methyl
acid
nuclear
particle
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O·埃利萨尔德
M·施密特
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BASF SE
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Aqueous formulations, comprising (A) at least one film-forming (co)polymer, (B) particles, with a core (a) and at least one shell (b) different from the core (a) and optionally (C) at least one hydrophobic agent.

Description

Aqueous formulation and uses thereof
The present invention relates to comprise the aqueous formulation of following component:
(A) at least a film forming addition (being total to) polymer,
(B) comprise the particle of nuclear (a) and at least one described nuclear (a) shell (b) in addition and optional
(C) at least a hydrophobizers.
The invention further relates to the purposes of aqueous formulation of the present invention.The invention further relates to a kind of method and a kind of method of producing them of aqueous formulation coated surfaces of the application of the invention.
For some years people obviously for treatment surface so that they are antifouling or be difficult to stain interested at least.The whole bag of tricks comprises provides texture structure to the surface, the protuberance that for example provides 5-100 μ m height and 5-200 μ m space to separate.The texture structure of seeking to imitate the lotus flower plant has been given on the surface, for example referring to WO 96/04123 and US 3,354,022.Yet, this method always unfeasible and it be not suitable for handling textile surface.
WO 04/74568 discloses and has a kind ofly handled the method for putting textile material in order by the aqueous fluid with at least a organic or inorganic solid that comprises at least a organic polymer and at least a particle form, and this organic or inorganic solid is present in this aqueous fluid with the mark of 5.5g/l at least.Silica gel, especially pyrogenic silica, recommended solid as particle form.
EP 1 283 296 discloses and has used the sheet structure of prepared coating coating textile as follows: with 50-80 weight % at least a be selected from matrix that for example potato starch and oxide material comprise adhesive, fluorinated polymer and suitable words auxiliary agent as silica gel, silica flour or kaolinic finely divided material (diameter is 0.5-100 μ m (at least 80 a weight % finely divided material)), 20-50 weight % apply as described in structure.
Yet the potato starch that EP 1 283 296 is recommended has specific solubility in aqueous fluid or flotation fluid, thereby can not control the diameter of potato starch particle in the coat operations process best.Especially under the situation of inoganic solids such as silica gel, observe certain agglomeration tendency, this is disadvantageous to application and makes that the setting of structural parameters is more difficult.
Further observe many situations that wherein have not enough washability sometimes by such textiles of said method coating.For example, if the textiles that washing is made soaked with sweat is then observed first washing anti-fouling effect reduction afterwards and basic disappearance the after several wash cycle.
They the purpose of this invention is to provide and to be used for coated surfaces, particularly textile surface, so that can have the preparaton of antifouling property subsequently.Another object of the present invention provides a kind of method of coated surfaces, and this method has been avoided above-mentioned shortcoming, particularly for the coating of textile surface.A further object of the present invention provides the coated surfaces of avoiding above-mentioned shortcoming and presenting good soil resistance.
We find that this purpose is realized by the defined aqueous formulation of beginning.
Starting defined aqueous formulation comprises:
(A) at least a film forming addition (being total to) polymer,
(B) comprise the particle of nuclear (a) and at least one described nuclear (a) shell (b) in addition and optional
(C) at least a hydrophobizers.
Aqueous formulation of the present invention comprises one or more film forming addition (being total to) polymer (A).Film forming addition (being total to) polymer (A) not only refers to disperse or (being total to) polymer of emulsification also refers to (organisoled) (being total to) polymer of organosol, for example polyacrylate, polyurethane, polybutadiene, polyolefin such as polyethylene or polypropylene and copolymer thereof, described film forming addition (being total to) polymer is owing to hot post processing or use radiation, especially the IR radiation treatment and can be on base material to be applied film forming, to not significantly infringement of base material.The dispersion of optimization polypropylene acid esters or polyurethane or emulsion.
The suitable polyacrylates that is preferably used as film forming addition of the present invention (being total to) polymer (A) is the addition copolymer of following monomer, particularly the emulsion addition copolymer: at least a C of at least a monoethylenically unsaturated carboxylic acid or dicarboxylic acids such as maleic acid, fumaric acid, crotonic acid, itaconic acid or preferred (methyl) acrylic acid and at least a comonomer such as at least a monoethylenically unsaturated carboxylic acid or dicarboxylic acids 1-C 10Arrcostab, particularly (methyl) methyl acrylate, ethyl acrylate, n-butylacrylate and 2-ethylhexyl acrylate, and/or at least a vinyl-arene that for example is selected from, for example p-methylstyrene, α-Jia Jibenyixi and particularly styrene, and nitrogenous comonomer is as other comonomers of (methyl) acrylamide, (methyl) acrylonitrile.
The reactive comonomer that can comprise in one embodiment of the invention, at least a being selected from (methyl) glycidyl acrylate, acetoacetyl (methyl) acrylate and N-methylol (methyl) acrylamide with copolymerized form as the polyacrylate of adhesive.
Be the hydroxy-end capped polyurethane that can obtain by at least a polyesterols and vulcabond or polyisocyanates and suitable other reactant reactions preferably as the suitable polyurethane of adhesive of the present invention, described polyesterols for example is aliphatic dicarboxylic acid such as butanedioic acid, glutaric acid and particularly adipic acid and at least a aliphatic diol, for example 1,6-hexylene glycol, 1, the condensation product of 4-butanediol, neopentyl glycol, ethylene glycol or diethylene glycol (DEG).Suitable vulcabond is aliphatic, alicyclic and aromatic diisocyanates, particularly hexamethylene diisocyanate (HDI), ten dimethylene diisocyanates, 4,4 '-diisocyanate based cyclohexyl-methane (MDI), cyclohexane-1,4-vulcabond, isophorone diisocyanate (IPDI) and aromatic diisocyanates such as toluene di-isocyanate(TDI) (TDI).
As other reaction partners, for example can mention glycol, particularly 1, the 4-butanediol also has sour functional molecules, particularly sour functional glycol and sour official can diamines, example is 3,3-dihydroxy hydroxymethyl propionic acid and
Figure A200780042698D00061
Aqueous formulation of the present invention further comprises and contains nuclear (a) and at least one nuclear (a) shell (b) and heat treated subsequently particle (B) in addition.
In one embodiment of the invention, the number average diameter of particle (B) is 20-1000nm, preferred 25-475nm, more preferably 50-300nm.Particle diameter for example can use conventional method such as transmission electron microscope to measure.
In one embodiment of the invention, the nuclear (a) of particle (B) has 10-950nm, preferably 450nm, the more preferably average diameter of 15-250nm at the most.
The thickness of nuclear number average diameter of (a) and shell (b) can be advantageously suitable by taking place in the preparation process of particle (B) by supposition, particularly transforms and use in each case density at nuclear (a) that does not exist other component-shells (b) or nuclear (a) to produce down and shell (b) as the average diameter of density measurement nuclear (a) and shell (b) and arithmetically definite completely.
In one embodiment of the invention, particle (B) has unimodal diameter distribution.In another embodiment of the present invention, particle (B) can have bimodal diameter and distribute.
One embodiment of the invention comprise that particle (B) does not neither exist with agglomerate with aggregate form yet.
One embodiment of the invention comprise that particle (B) has irregularly shaped.Preferred particulates (B) has regular shape, and is for example oval or especially spherical.
Nuclear (a) and shell (b) preferably comprise organic copolymer separately.
Nuclear (a) is different mutually with shell (b).In one embodiment of the invention, nuclear (a) comprises different organic copolymers with shell (b), i.e. different copolymer on quantity or chemical constitution for example.In another embodiment of the present invention, nuclear (a) comprises by same comonomer but with the different organic copolymers of different copolymer monomer than preparation with shell (b).
In one embodiment of the invention, nuclear (a) and shell (b) are covalently bound mutually.
In a particular embodiment of the present invention, particle (B) comprises core-shell polymer, and shell is corresponding to shell (b).
In one embodiment of the invention, nuclear (a) comprises the cross-linked copolymer of at least a alefinically unsaturated compounds, for example vinyl aromatic compounds or (methyl) acrylic acid C 1-C 10The copolymer of Arrcostab.One or more crosslinking agents for example can be used as comonomer.Other comonomers that suitable words can be used for preparation nuclear (a) comprise the compound that one or more can be free-radical polymerized with alefinically unsaturated compounds, and example is (methyl) acrylic acid C 1-C 10Arrcostab, (methyl) acrylic acid ω-hydroxyl-C 2-C 4Alkylene ester, monoethylenically unsaturated carboxylic acid does not replace or by C 1-C 10Alkyl or two-C 1-C 10Positive alkyl-C 2-C 4The alkylidene list-or disubstituted (methyl) acrylamide, especially N, N-dimethylaminopropyl Methacrylamide (DMAPMAM).
The example of suitable vinyl aromatic compounds for example is α-Jia Jibenyixi, p-methylstyrene, 2,4-dimethyl styrene and especially styrene.
Specially suitable (methyl) acrylic acid C 1-C 20The example of Arrcostab is (methyl) n-butylacrylate and methyl methacrylate.
Useful crosslinking agent for example comprises two-and trivinyl aromatic hydrocarbons, for example adjacent divinylbenzene, between divinylbenzene and to divinylbenzene, (methyl) acrylate of binary or trihydroxylic alcohol, example is ethylene glycol bisthioglycolate (methyl) acrylate, 1, ammediol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,1,1-trimethylolpropane two (methyl) acrylate, 1,1,1-trimethylolpropane tris (methyl) acrylate also has (methyl) acrylic acid allyl ester and (methyl) glycidyl acrylate.
Suitable (methyl) acrylic acid C 1-C 10The example of Arrcostab is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-pro-pyl ester, (methyl) acrylic acid isopropyl esters, (methyl) n-butylacrylate, (methyl) acrylic acid n-hexyl ester, (methyl) 2-ethylhexyl acrylate, the positive decyl ester of (methyl) acrylic acid.
Suitable (methyl) acrylic acid ω-hydroxyl C 2-C 4The example of alkylene ester is (methyl) acrylic acid 4-hydroxybutyl ester, (methyl) acrylic acid 3-hydroxy-propyl ester and especially (methyl) acrylic acid 2-hydroxyethyl ester.
Specially suitable monoethylenically unsaturated carboxylic acid for example is maleic acid, fumaric acid, trans and cis crotonic acid, itaconic acid and especially acrylic acid and methacrylic acid.
C 1-C 10Alkyl-or two C 1-C 10Amino positive alkyl C 2-C 4The alkylidene list-or the example of dibasic (methyl) acrylamide be N-methyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N, N-dimethyl aminoethyl (methyl) acrylamide and N, N-dimethylaminopropyl (methyl) acrylamide.
The organic cross-linked copolymer that is used for nuclear (a) for example can use 25mol% at the most, preferably 20mol% and 1mol% crosslinking agent and 75mol% at least at the most at least, preferably at least 80mol% and more preferably at the most one or more above-mentioned monoene of 99mol% belong to the unsaturated comonomer preparation.
In one embodiment of the invention, particle (B) also comprises the shell (b) of the crosslinked or crosslinkable copolymer of the ester that for example comprises at least a ethylenically unsaturated carboxylic acids or at least a ethylenically unsaturated carboxylic acids or acid amides.
In one embodiment of the invention, particle (B) comprises the ester that for example comprises at least a ethylenically unsaturated carboxylic acids or at least a ethylenically unsaturated carboxylic acids or the shell crosslinked or further crosslinked copolymers (b) of acid amides, and promptly this shell comprises so-called early stage cross-linked copolymer.
In order to realize the crosslinked of shell (b), one or more in the above-mentioned crosslinking agent can be copolymerized in the described copolymer, for example based on the gross weight of particle (B) 7 weight % at the most, preferred 0.1-5 weight %.
The crosslinkable copolymer is interpreted as referring to for example reacting and that crosslinked analog copolymer of result under the heat-treat condition in another step of the inventive method.For example, suitable is to comprise one or more with copolymerized form to have epoxide group, NH-CH 2That analog copolymer of the comonomer of OH group or acetoacetyl.
The list that specially suitable comonomer with epoxide group for example is itaconic acid, maleic acid, fumaric acid-or 2-glycidyl ester, the ethylene oxidic ester of E-and Z-crotonic acid and especially acrylic acid and methacrylic acid in addition.
Specially suitable have a NH-CH 2The comonomer of OH group for example is product, especially N hydroxymethyl acrylamide and the N-methylol methacrylamide that formaldehyde and monoene belong to unsaturated carboxylic acid amides.
Specially suitable comonomer with acetoacetyl group for example is (methyl) acrylate of the alcohol of general formula I:
Figure A200780042698D00091
Wherein
R 1Be selected from branching or nonbranched C 1-C 10Alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, neopentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohesyl, Sec-Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl, more preferably nonbranched C 1-C 4Alkyl such as methyl, ethyl, n-pro-pyl and normal-butyl.
Other suitable comonomer of preparation shell (b) for example are vinyl aromatic compounds, (methyl) acrylic acid C 1-C 10Arrcostab, (methyl) acrylic acid ω-hydroxyl C 2-C 4Alkylene ester and (methyl) acrylic acid.
In one embodiment of the invention, nuclear (a) or shell (b) or nuclear (a) comprise a kind of anionic copolymer or different anionic copolymers with shell (b).Anionic copolymer the context of the invention be meant by can radical polymerization and one of them (so-called anionic copolymerization monomer) per molecule have that analog copolymer of at least one alefinically unsaturated compounds that can in aqueous formulation, take off the group of proton (example is methacrylic acid or vinyl phosphonate) preparation.
In another embodiment of the present invention, nuclear (a) or shell (b) or nuclear (a) comprise a kind of cation copolymer or different cation copolymers with shell (b).Cation copolymer the context of the invention be meant by can radical polymerization and one of them (so-called cationic comonomer) per molecule have at least one can be in aqueous formulation protonated group such as one or more that analog copolymer that has the right nitrogen-atoms of free electron or cation group as the alefinically unsaturated compounds preparation that is attached to the quaternary nitrogen atoms in the polymer chain.
Cation copolymer for example can relate to and have free amine group, for example NH 2Group, NH (C 1-C 4Alkyl) group, N (C 1-C 4Alkyl) 2Group or (C 1-C 4Alkyl) 2N-C 2-C 10Alkylidene, especially (CH 3) 2N-C 2-C 4That analog copolymer of alkylidene.
In one embodiment of the invention, under acid condition, for example be 6 or littler pH under cation copolymer so that the small part protonated form exist.
In one embodiment of the invention, cation copolymer can be thought to comprise one or more acid amides of at least a ethylenically unsaturated carboxylic acids as (methyl) acrylamide that analog copolymer as one of comonomer with copolymerized form.
In one embodiment of the invention, cation copolymer is by at least a non-ionic co-monomers, for example at least a C of vinyl aromatic compounds such as styrene or at least a ethylenically unsaturated carboxylic acids 1-C 20Arrcostab and at least a per molecule have at least one can be protonated or the copolymer that constitutes of the comonomer of quaternized nitrogen-atoms.
Cation copolymer in implication of the present invention can also comprise one or more anionic copolymerization monomers as (methyl) acrylic acid or crotonic acid by copolymerized form.When cation copolymer also comprises at least a anionic monomer with copolymerized form, the molar fraction of cationic comonomer always is higher than the molar fraction of anionic copolymerization monomer, for example based on total cation copolymerization object height 0.5mol%, preferably 1mol%, more preferably 1.5-20mol% at least.
In one embodiment of the invention, shell (b) perhaps is present in crosslinked in the shell (b) or glass transition temperature T that the crosslinkable copolymer has gBe-50 ℃ to+30 ℃, preferred-20 ℃ to+30 ℃.
The particle (B) that comprises nuclear (a) and at least one nuclear (a) shell (b) in addition can prepare in every way, for example by using the multistage emulsion polymerisation of one or more radical initiators in the presence of one or more emulsifying agents or the emulsion polymerization prepared by gradient mode.Nuclear (a) is using the synthetic shell (b) of comonomer composition that changes synthetic before.Preferred nuclear (a) is by the emulsion polymerization prepared of spermotype; Promptly at first with very little particle, for example number average diameter is that the particle of 10-30nm adds one or more insoluble polymers such as polystyrene, promotes in polymerization process that then drop forms.
Aqueous formulation of the present invention can further comprise at least a hydrophobizers (C).
In one embodiment of the invention, hydrophobizers (C) is selected from:
(C1) halogen-containing organic (being total to) polymer,
(C2) alkane,
(C3) per molecule has at least one C 10-C 60The compound of alkyl and
(C4) polysiloxanes.
Useful halogen-containing (being total to) polymer (C1) for example comprise can be preferably single or many halos, preferred chloro and the more preferably chlorination for preparing of free radical (being total to) polymerization of fluoro (copolymerization) monomer and especially fluoridize (being total to) polymer by one or more.
Halogen-containing (copolymerization) monomer very particularly preferably is Fluorine containing olefine such as vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropene, fluoridizes or perfluorinate C 3-C 11The vinyl esters of carboxylic acid, for example as US 2,592,069 and US 2,732, described in 370, fluoridize or perfluorinated alcohols as fluoridizing or perfluorinate C 3-C 14(methyl) acrylate of alkylol, for example HO-CH 2-CH 2-CF 3, HO-CH 2-CH 2-C 2F 5, HO-CH 2-CH 2-n-C 3F 7, HO-CH 2-CH 2-different-C 3F 7, HO-CH 2-CH 2-n-C 4F 9, HO-CH 2-CH 2-n-C 6F 13, HO-CH 2-CH 2-n-C 8F 17, HO-CH 2-CH 2-O-n-C 6F 13, HO-CH 2-CH 2-O-n-C 8F 17, HO-CH 2-CH 2-n-C 10F 21, HO-CH 2-CH 2-n-C 12F 25(methyl) acrylate, for example US 2,642,416, US 3,239,557 and US 3,462, described in 296.
Useful copolymer for example further comprises (methyl) acrylic acid and/or (methyl) acrylic acid C 1-C 20The copolymer of the ester of Arrcostab or (methyl) glycidyl acrylate and formula II:
Figure A200780042698D00111
Wherein
R 2Be CH 3, C 2H 5,
R 3Be hydrogen, CH 3, C 2H 5,
X is 4-12, the integer of preferred 6-8,
Y is 1-11, the integer of preferred 1-6,
Or the copolymer of the vinyl esters of (methyl) glycidyl acrylate and fluorinated carboxylic can be used as polymer containing halogen (C).
Useful hydrophobizers (C) further comprises fluoridizes, especially perfluorinate C 3-C 12(methyl) acrylate of alkylol and non-halo C 1-C 20The copolymer of (methyl) acrylate of alcohol, described perfluorinate C 3-C 12Alkylol for example is HO-CH 2-CH 2-CF 3, HO-CH 2-CH 2-C 2F 5, HO-CH 2-CH 2-n-C 3F 7, HO-CH 2-CH 2-iso-C 3F 7, HO-CH 2-CH 2-n-C 4F 9, HO-CH 2-CH 2-n-C 6F 13, HO-CH 2-CH 2-n-C 8F 17, HO-CH 2-CH 2-O-n-C 6F 13, HO-CH 2-CH 2-O-n-C 8F 17, HO-CH 2-CH 2-n-C 10F 21, HO-CH 2-CH 2-n-C 12F 25, described non-halo C 1-C 20(methyl) acrylate of alcohol for example is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butylacrylate, (methyl) acrylic acid n-pro-pyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) acrylic acid n-octyl ester, the positive decyl ester of (methyl) acrylic acid, (methyl) acrylic acid dodecyl ester, (methyl) acrylic acid n-eicosane base ester.
Can be as the summary of other fluorinated polymers of halogen-containing organic (being total to) polymer (C1) or copolymer for example people such as M.Lewin, Chemical Processing of Fibers and Fabrics, the B part, the 2nd volume, Marcel Dekker, New York (1984), the 172nd page and find in each page and the 178-182 page or leaf subsequently.
Other can for example be described among the DE 199 120 810 as (being total to) polymer of fluoridizing of halogen-containing organic (being total to) polymer (C1).
The inventive method can use a kind of halogen-containing (being total to) polymer (C1) or multiple different halogen-containing (being total to) polymer (C1) to carry out.
Halogen-containing (being total to) polymer (C1) preferably is used to implement the inventive method with uncrosslinked form, but can be in dry run that it is crosslinked.
Other suitable hydrophobizers (C) are alkane (C2).Alkane (C2) for example can at room temperature be liquid or solid and be natural or preferred synthetic.Preferred alkane (C2) is synthetic alkane such as Fischer-Tropsch (Fischer-Tropsch) wax, for example use the high density polyethylene waxes of Z-N (Ziegler-Natta) catalyst or metallocene catalysts, the high density polyethylene waxes (acid number of measuring according to DIN53402 is a 1-150mg KOH/g alkane) that also has partial oxidation, wherein high density polyethylene waxes not only comprises the homopolymers wax of ethene but also comprises and has at the most 20 weight % comonomers altogether (as propylene, the 1-butylene, the 1-amylene, the 1-hexene, the 1-octene, 1-decene or 1-dodecylene) poly copolymer, especially so-called paraffin and different paraffin, for example thick alkane (scale wax), the slack wax raffinate, thick alkane (scale wax deoils) deoils, half-or refining fully alkane (half-or complete refined paraffin wax) and bleaching alkane (bleaching paraffin).Paraffin refers in particular under the room temperature for solid and at 40-80 ℃ at this paper, the alkane of fusing in the preferred 50-75 ℃ of scope, i.e. and branching or nonbranched ring-type or preferred acyclic saturated hydrocarbons, separately or be preferably the mixture of multiple saturated hydrocarbons.Paraffin preferably is made up of the saturated hydrocarbons with 18-45 carbon atom in the context of the invention.Isoparaffin preferably is made up of the saturated hydrocarbons that per molecule has a 20-60 carbon atom in the context of the invention.
Useful hydrophobizers (C) comprises that further per molecule has at least one C 10-C 60Alkyl, preferred C 12-C 40The linearity of alkyl or heterocycle, preferred heteroaromatics (C3) hereinafter also is abbreviated as compound (B3), wherein C 10-C 60Alkyl is different or preferred identical and is branching or preferably nonbranched.Preferably can be when the temperature that is heated to 120-200 ℃ separating out at least one fatty amine or at least a fatty alcohol, promptly have C 10-C 60That compounds (C3) of the amine of alkyl or alcohol.
The compound of general formula III very particularly preferably:
Figure A200780042698D00131
Wherein
R 4Be selected from branching or preferred nonbranched C 10-C 60Alkyl, for example n-C 10H 21, n-C 12H 25, n-C 14H 29, n-C 16H 33, n-C 18H 37, n-C 20H 41, n-C 30H 61, n-C 40H 81, n-C 50H 101, n-C 60H 121, and CH 2OR 10, R wherein 10Be selected from branching or preferred nonbranched C 10-C 60Alkyl, for example n-C 10H 21, n-C 12H 25, n-C 14H 29, n-C 16H 33, n-C 18H 37, n-C 20H 41, n-C 30H 61, n-C 40H 81, n-C 50H 101, n-C 60H 121Carbon number and corresponding hydrogen number are thought of as mean value.
R 5-R 9Different or preferred identical and be selected from hydrogen, R 4, CH 2-OH, CH 2-O-C 1-C 10Alkyl, especially CH 2-OCH 3, CH 2-OC 2H 5, CH 2-O-n-C 4H 9, CH 2-OCH 2CH 2OH, CH 2-OCH 2CH 2O-C 1-C 10Alkyl, particularly CH 2-OCH 2CH 2OCH 3, CH 2-OCH 2CH 2OC 2H 5, CH 2-OCH 2CH 2O-n-C 4H 9, CH 2-(OCH 2CH 2) 2O-H, CH 2-(OCH 2CH 2) 2O-C 1-C 10Alkyl, especially CH 2-(OCH 2CH 2) 2OCH 3, CH 2-(OCH 2CH 2) 2OC 2H 5And CH 2-(OCH 2CH 2) 2O-n-C 4H 9
The compound that other special preferred embodiments of compound (C3) are general formula I V:
Figure A200780042698D00132
Wherein variable separately as defined above.
The example of polysiloxanes (C4) is the compound of general formula V:
Figure A200780042698D00141
Wherein
R 14Be selected from Si (CH 3) 3And hydrogen,
X is selected from C 1-C 4Alkyl, particularly methyl and
Hydrogen,
Epoxide group, particularly
NH 2, amino alkylidenyl, preferred omega-amino-alkylidene, particularly (CH 2) w-NH 2, wherein w is 1-20, preferred 2-10, and one or more preferred non-adjacent CH 2Group can be replaced by oxygen or NH.The example of X is CH 2-NH 2, CH 2CH 2-NH 2, (CH 2) 3-NH 2, (CH 2) 4-NH 2, (CH 2) 6-NH 2, (CH 2) 3-NH-(CH 2) 2-NH 2, (CH 2) 2-NH-(CH 2) 3-NH 2
[Si (CH 3) 2-O] and [SiX (CH 3)-O] unit can block or random setting.
M and the n integer of respectively doing for oneself.The summation of n and m can be 30-2000, preferred 50-1500.
Preferred m is greater than n.More preferably n is 1-10, and particularly working as X is not CH 3The time, and correspondingly select m.
In one embodiment of the invention, the dynamic viscosity of polysiloxanes (C4) is 100-50000mPa.s when measuring down for 23 ℃, particularly works as X=CH 3And R 14=Si (CH 3) 3The time.
One embodiment of the invention utilization comprises the hydrophobizers (C) of the combination of at least a alkane (C2) and at least a compound (C3).
Aqueous formulation of the present invention can aqueous suspension, emulsion or dispersion, and preferred aqueous fluid form exists.
The solids content that aqueous formulation of the present invention, particularly aqueous fluid may have is 10-70 weight %, preferred 30-50 weight %.
In one embodiment of the invention, aqueous formulation, preferred aqueous fluid has 2-9, the pH of preferred 3.5-7.5.
The present invention further provides the purposes of aqueous formulation of the present invention in coated surfaces.The present invention further provides a kind of method of aqueous formulation coated surfaces of the application of the invention, hereinafter be also referred to as coating method of the present invention.
Coating method of the present invention can contact with aqueous formulation of the present invention by making the surface, stands it and acts on also subsequent drying and carry out.
For the purpose of the present invention, the surface can be constituted and belonged to any required goods by any material requested.The surface of preferred flexible base material.The especially preferred surface of forming by fibrous material such as paper, plate, leather, dermatine, Alcantara, more particularly the surface is a textile surface, promptly they are textile surfaces.
For the purpose of the present invention, textiles is fabric fibre, fabric intermediate and finished product and by the finished product of its manufacturing, except clothing industry with also comprising for example carpet and other household textiless and the fabric structure thing that is used for industrial purposes the textiles.These comprise the structure such as the staple fibre of not moulding, lineament thing such as cord, long filament, yarn, line, rope, lace, band, rope, and three-dimensional structure thing such as felt, weaven goods, nonwoven and liner.For the purpose of the present invention, textiles can be a natural origin, example is cotton, wool or flax, or synthetic, example is polyamide, polyester, modified poly ester, polyester blend fabric, polyamide BLENDED FABRIC, polyacrylonitrile, triacetate, acetic acid esters, Merlon, polypropylene, polyvinyl chloride, polyester microfiber and glass fabric.The preferred especially textiles of forming by cotton.
Coating method of the present invention makes and can apply a surface (side, front) according to the present invention and another surface does not apply, and perhaps can apply two surfaces (side, front) by the inventive method.May reasonably be by the inventive method coating outer surface for example, and interior (towards health) surface apply to some clothes such as Work Clothes; And may reasonably be to apply some industrial textiles such as the fluffy two sides (front and back) of canvas on the other hand by the inventive method.
The temperature itself of implementing coating is unimportant.This temperature can be 10-60 ℃, preferred 15-30 ℃.
In one embodiment of the invention, coating method of the present invention for example can spray, spray, pour into a mould by single or multiple, printing, plasma-deposited or pad and carry out.
For by using aqueous fluid or flotation fluid to come contact surface to implement coating method of the present invention, wet pickup can be selected so that the wet pickup that the inventive method obtains is 25-95 weight %, preferred 60-90 weight %.
Coating method of the present invention carries out in being usually used in the machine of textile finishing in a preferred embodiment of the invention, and example is a padder.Preferred vertical charging padder, wherein necessary element are two rollers of pressing contact each other, introduce textiles by this roller.Preferred moisture preparaton is filled on the above-mentioned roller and wetting textiles.Pressure makes textiles be squeezed and guarantees constant liquid absorption.In other preferred padders, at first dipping bath is passed through in the textiles guiding, upwards pass through two rollers of pressing contact each other then.Under one situation of back, padder also has textiles charging vertically upward.Padder for example is described in Hans-Karl Rouette, and " Handbuch derTextilveredlung " is in Deutscher Fachverlag 2003, the 618-620 pages or leaves.
In one embodiment of the invention, coating method of the present invention can contact heat treatment and implementing then by making the surface with at least a aqueous formulation of the present invention.
After the coating surface is heat-treated.Heat treatment may be carried out drying.Heat treatment also may be carried out cross-linking reaction.Preferred heat treatment is carried out under the temperature below the fusing point of nuclear (a).
In one embodiment of the invention, heat treatment can for example carried out under 20-200 ℃ the temperature.
Heat treatment for example can be carried out under atmospheric pressure.It can also for example carry out under the pressure of 1-850 millibar in decompression.
Heat treatment can utilize heating or heated air stream not, especially heating or the inert gas of not heating such as the air-flow of nitrogen.In order to utilize heated air stream, suitable temperature range for example is 30-200 ℃, preferred 120-180 ℃, and more preferably 150-170 ℃.
Heat treatment can be carried out continuously or in batches.The heat treatment duration can be selected in wide region.Heat treatment can be carried out about 1 second to about 30 minutes usually, especially 10 seconds to 3 minutes time.
In one embodiment of the invention, heat treatment can be carried out in two or more steps, in this case first step is selected than second step and the suitable low treatment temperature of words later step.
Hot-air dry is the example of heat treated concrete appropriate method.
One embodiment of the invention comprise by utilizing and comprise at the most the aqueous formulation of one or more auxiliary agents (D) of 10 weight % based on whole preferred moisture preparaton and implement the inventive method.Especially in the time will handling one or more textile surface, may preferably introduce one or more auxiliary agents (D) in preferred moisture preparaton for the purpose of the present invention, auxiliary agent (D) is selected from biocide, thickener, foam inhibitor, wetting agent, plasticizer, feel modifier, filler, crosslinking agent (curing agent) and film forming agent in this case.
The example that can be used as the biocide of auxiliary agent (D) is 1,2-benzisothiazole-3-ketone (BIT) (with
Figure A200780042698D0017161321QIETU
The trade mark is commercial by Avecia Lim.) and alkali metal salt; Other suitable biocides are 2-methyl-2H-isothiazole-3-ketone (MIT) and 5-chloro-2-methyl-2H-isothiazole-3-ketone (CIT).Just much of that based on the biocide that preferred moisture preparaton is generally 10-150ppm.
Useful auxiliary agent (D) further comprises one or more thickeners, and it can be natural or synthetic source.Suitable synthetic thickening agent is poly-(methyl) acyclic compound, polycarboxylic acids, polyethers, poly-imines, polyamide and polyurethane, especially comprises the copolymer of (methyl) acrylamide derivative of 85-95 weight % acrylic acid, 4-15 weight % acrylamide and about 0.01-1 weight % formula VI:
Figure A200780042698D00171
Its molecular weight M wBe 100000-200000g/mol, each R 11Be methyl or preferred hydrogen.The example of the thickener of natural origin is agar, carrageenan, modified starch and modified cellulose.
The amounts of thickener that comprises can be 0-10 weight % based on used aqueous formulation in the inventive method for example, preferred 0.05-5 weight %, more preferably 0.1-3 weight %.
The example that can be used as the foam inhibitor of auxiliary agent (D) is to be the polysiloxanes of liquid under the room temperature, and it is not by ethoxylation or coverlet ethoxylation or many ethoxylations.
The example that can be used as the wetting agent of auxiliary agent (D) is alkyl poly glucoside, alkyl phosphonates, phosphonic acids alkyl phenyl ester, alkylphosphonate and alkyl phenyl phosphate ester.
The example that can be used as the plasticizer of auxiliary agent (D) is to be selected from by the aliphatic series of the complete esterification of alkanol or aromatics two-or the polycarboxylic acid and ester compounds of the phosphoric acid of strand alkanol esterification at least.
Alkanol is C in one embodiment of the invention 1-C 10Alkanol.
By the aromatics two of the complete esterification of alkanol-or polycarboxylic preferred embodiment be phthalic acid, M-phthalic acid and the mellitic acid of complete alkanol esterification; Instantiation is phthalic acid di-n-octyl ester, phthalic acid two n-nonyl esters, phthalic acid two positive decyl ester, M-phthalic acid di-n-octyl ester, M-phthalic acid two n-nonyl esters, M-phthalic acid two positive decyl ester.
By the aliphatic series two of the complete esterification of alkanol-or polycarboxylic preferred embodiment for example be dimethyl adipate, diethylene adipate, adipic acid-di-n butyl ester, adipic acid diisobutyl ester, dimethyl glutarate, ethyl glutarate, glutaric acid di-n-butyl ester, glutaric acid diisobutyl ester, dimethyl succinate, diethyl succinate, butanedioic acid di-n-butyl ester, butanedioic acid diisobutyl ester and composition thereof.
At least the preferred embodiment of the phosphoric acid of strand alkanol esterification is phosphoric acid C 1-C 10Alkyl two-C 6-C 14Aryl ester such as phosphoric acid isodecyl diphenyl.
Other suitable example of plasticizer are at least by C 1-C 10The aliphatic series of alkyl carboxylic acid mono-esterification or aromatics two-or polyalcohol.
At least by C 1-C 10The aliphatic series of alkyl carboxylic acid mono-esterification or aromatics two-or the preferred embodiment of polyalcohol be 2,2,4-trimethylpentane-1,3-glycol mono isobutyrate.
Other suitable manufacturing methods are can be by aliphatic dicarboxylic acid and aliphatic diol, for example adipic acid or butanedioic acid and 1, the polyester that the polycondensation of 2-propylene glycol obtains, preferably its M wBe 200g/mol, and polypropylene glycol alkyl phenyl ether, preferably its M wBe 450/mol.
Other suitable manufacturing methods are by two kinds of pure etherificates of difference and molecular weight M wBe the polypropylene glycol of 400-800g/mol, wherein preferred a kind of alcohol can be alkanol, especially C 1-C 10Alkanol, and another kind of alcohol can be preferably aromatic alcohol, for example orthoresol, metacresol, paracresol and especially phenol.
The examples of fillers that can be used as auxiliary agent (D) is the melamine and the pigment of particle form.
The example that can be used as the feel improver of auxiliary agent (D) is a polysiloxane emulsion, promptly can preferably have the aqueous emulsion of the polysiloxanes of hydrophilic radical such as OH group or alkoxylate groups.
The example that can be used as the crosslinking agent (curing agent) of auxiliary agent (D) is the condensation product of urea, glyoxal and formaldehyde, and suitable words are by preferred linear C 1-C 4The alkanol etherificate, the following formula: compound of especially dual, triple or quadruple etherificate by methyl alcohol or ethanol:
Figure A200780042698D00181
The crosslinking agent (curing agent) that can be used as auxiliary agent (D) further comprises isocyanuric acid ester, especially vulcabond/the isocyanuric acid ester of the isocyanuric acid ester of hydrophiling and mixing hydrophiling, for example C 1-C 4The product of the isocyanuric acid ester of alkyl polyethylene glycol and hexamethylene diisocyanate (HDI).The example of this class suitable crosslinking agents is for example known by EP-A 0 486 881.
Diethylene glycol (DEG) is the example of the film forming agent (coalescents) that can be used as auxiliary agent (D).
In another embodiment of the present invention, surface to be applied provided priming paint (E) before the reality coating, and then at least a aqueous formulation of the present invention is provided.Priming paint (E) preferably give treat according to the surface of the present invention coating with electric charge (seeing below), the especially electric charge of the opposite charge of its shell (b) of particle (B).For example when use has such particle (B) of CATION shell (b), advantageously use anion priming paint (E).Yet, when use has such particle (B) of anion shell (b), advantageously use cationic primer (E).
Suitable priming paint (E) for example can be for polymerization or unpolymerized in nature.Suitable polymerization priming paint for example can have the number-average molecular weight of 5000-500000g/mol.
Useful cationic primer (E) for example comprises that polymine and especially amino silicone are as having at least one (CH 2) wNH-R 12The siloxanes of group, wherein w is integer and the R of 1-10, especially 2-7 12Be selected from hydrogen, preferred linear C 1-C 4Alkyl and (CH 2) wNH-R 13, R wherein 13Be selected from hydrogen and preferred linear C 1-C 4Alkyl also has polyvinyl imidazol.Other suitable cationic primer (E) are diallyl two-C 1-C 4The polymer of alkyl ammonium halide, wherein each C 1-C 4It is linear that alkyl preferably is.
The diamines of the preferred ring-type that other suitable cationic primer (E) are equimolar amountss and chloropropylene oxide and alkylating agent such as dimethyl suflfate, C 1-C 10The product of alkyl halide, particularly iodomethane, or benzyl halide, especially benzyl chloride.Such product can have the molecular weight M of 1000-1000000g/mol wAnd be constructed as follows, illustrate as an example with reference to the piperazine of equimolar amounts and the product of chloropropylene oxide and benzyl chloride:
Suitable anion priming paint (E) for example is anionic monomer, especially olefinic unsaturated sulfonic acid, olefinic unsaturated amine oxide or (methyl) acrylic acid homopolymers, suitable words and one or more (methyl) acrylic acid C 1-C 10The copolymer of Arrcostab.Other suitable anion priming paint for example are anion polyurethane, and promptly per molecule comprises that class polyurethane of at least one sulfonic acid group or hydroxy-acid group herein, and it for example can use 1, the preparation of 1-dihydromethyl propionic acid.
In order to use one or more priming paint (E), preferably it is being used with the aqueous formulation use and before with particle (B) coating.Suitable operating technology for example comprises spraying, spray and especially pads.
Priming paint (E) use and the coating of film forming addition (being total to) polymer (A) and particle (B) can be carried out before heat treatment and afterwards respectively, the heat-treat condition under every kind of situation is corresponding to above-mentioned condition.
One embodiment of the invention comprise cationic primer (E) are applied on the cotton surface, suitable words heat treatment and subsequently with aqueous formulation coating of the present invention.Another embodiment of the present invention comprises not to cotton surface applied priming paint (E) and directly with aqueous formulation coating of the present invention.Heat-treat in each case after this.
Another embodiment of the present invention comprises anion priming paint (E) is applied on the surface of polyester, suitable words heat treatment and subsequently with aqueous formulation coating of the present invention.Heat-treat after this.
The present invention further provides the coated surfaces of producing by the inventive method.
The particle (B) of nuclear (a) and at least one described nuclear (a) shell (b) in addition and the surface of optional at least a hydrophobizers (C) have been the present invention further provides and have scribbled film forming (being total to) polymer (A), comprised.
Surface of the present invention can be advantageously by said method production of the present invention.Surface of the present invention has texture structure, refuses water and is difficult for staining.
One embodiment of the invention comprise any adjuvant used (D), and they are if the words of using only are applied to the present invention surface with trace and therefore are not present in the coated surfaces of the present invention substantially.
In one embodiment of the invention, surface of the present invention is characterised in that to handle and causes the coating possibility inhomogeneous or evenly preferred.Evenly be interpreted as fingerprint reason tactical rule, and the inhomogeneous texture structure that is meant is irregular, promptly has textured region and non-textured region from the teeth outwards.
In one embodiment of the invention, it is 50nm-5 μ m that surface of the present invention comprises average thickness, preferred 100nm-1 μ m, the more preferably coating of 500nm at the most.
In one embodiment of the invention, the liquid absorption that has of the coating of using according to the present invention is 0.2-10g/m 2, preferred 1-2g/m 2
In one embodiment of the invention, the present invention surface is a textile surface.Textile surface of the present invention not only has excellent hydrophobic property and soil resistance, and has favorable durability, especially washing resistance or washable boiling hot property.
The present invention further provides the method for a kind of production aqueous formulation of the present invention, production method hereinafter referred to as of the present invention.Production method of the present invention can be undertaken by following component and water are mixed with any order together:
(A) at least a film forming addition (being total to) polymer,
(B) comprise the particle of nuclear (a) and at least one described nuclear (a) shell (b) in addition,
(C) optional at least a hydrophobizers and
(ID) optional at least a auxiliary agent.
The production of film forming addition (being total to) polymer itself is known.Hydrophobizers (C) and auxiliary agent (D) are as mentioned above.
Particle (B) for example can for example pass through the substep emulsion polymerisation or pass through the emulsion polymerization prepared of pattern in gradient by emulsion polymerisation.
The nuclear (a) of production particle (B) and the suitable comonomer of shell (b) are as mentioned above.
Producing the emulsion polymerisation of particle (B) preferably uses at least a initator to carry out.At least a initator can be a peroxide.The example of suitable peroxides is alkali metal peracetic dithionite such as sodium peroxydisulfate, peroxo disulfate acid ammonium, hydrogen peroxide, organic peroxide such as diacetyl peroxide, di-t-butyl peroxide, the peroxidating diamyl, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, peroxidating two (o-tolyl), succinyl peroxide, the peracetic acid tertiary butyl ester, cross the maleic acid tertiary butyl ester, cross the isobutyric acid tertiary butyl ester, cross the neopentanoic acid tertiary butyl ester, cross sad tertiary butyl ester, cross the neodecanoic acid tertiary butyl ester, t-butyl perbenzoate, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, peroxide-2 ethyl hexanoic acid tertiary butyl ester and peroxide diamino acid diisopropyl ester.Also suitable is azo-compound such as azodiisobutyronitrile, azo two (2-amidine propane) dihydrochloride and 2,2 '-azo two (2-methylbutyronitrile).
Redox initiator is fit to carry out manufacture method of the present invention equally, and it for example is made up of peroxide and oxidable sulphur compound.Very particularly preferably close bisulfites and organic peroxide such as uncle C by acetone 4H 9-OOH, Na 2S 2O 5(sodium pyrosulfite) and organic peroxide such as uncle-C 4H 9-OOH or NaO-CH 2SO 2H and organic peroxide such as uncle C 4H 9The system that-OOH forms.Similarly, especially preferably such as ascorbic acid/H 2O 2System.Can be 20-105 ℃ to carrying out the selected temperature of manufacture method of the present invention, preferred 50-85 ℃.Advantageously the temperature of Xuan Zeing depends on the resolution characteristic of used initator.
The pressure condition that carries out preparation method of the present invention is unimportant usually, and for example the pressure of atmospheric pressure to 10 crust is suitable.
Production method of the present invention can use at least a emulsifying agent to carry out, this emulsifying agent can be anion, CATION or nonionic and be selected from as cited those of emulsifying agent (C).
Carrying out the selected duration of production method of the present invention can be 30 minutes to 12 hours, preferred 2-6 hour.
Various programs can select to be used to carry out preparation method of the present invention, for example (discontinuous) operation at intermittence or semicontinuous method or continuation method such as incoming flow charging process fully, and the latter also can the segmented model operation.
For example the seed routine described in EP 0 810 831 also can be used.Seed routine is effective especially for the particle (B) that production has the size distribution of good especially reproducibility.
Very particularly preferably at first by emulsion polymerization prepared nuclear (a).Nuclear (a) produces with particle form in reactant mixture.Yet, nuclear (a) is not purified and reactant mixture and comonomer, suitable other initators of words and suitable words emulsifier and in this way generation directly be aggregated to shell (b) on the nuclear (a).
Not preferred any particular theory, as if reasonably be shell (b) and nuclear (a) not only physics interconnects in many cases, and the mutual keyed jointing of covalency.
In one embodiment of the invention, it is smelly to dispel afterwards at preparation particle (B), for example by carrying out chemistry and dispel smelly at the reinforced back further initator of adding of finishing of comonomer.
The present invention is by work embodiment explanation.
Glass transition temperature T gUse has the Mettler-Toledo TA8200 series DSC822 differential scanning calorimetry (DSC) of TSO 801RO sample manipulator and measures.Differential scanning calorimetry (DSC) is equipped with the FSR5 temperature sensor.Method according to DIN 53765 is measured.
Estimate based on second heating curves under every kind of situation.Be cooled to-110 ℃ in each case, the rate of heat addition: 20 ℃/min, be heated to 150 ℃, under 150 ℃, kept 5 minutes, be cooled to-110 ℃ then, the rate of heat addition: 20 ℃/min, be heated to 150 ℃.
The particle diameter of particle (B) distributes and uses the MalvernCoulter counter to measure according to ISO 13321 in each case.
I. prepare film forming addition (being total to) polymer (A), particle (B) and preparaton of the present invention
I.1. prepare film forming addition (being total to) polymer (A.1)
Prepare following mixture:
Mixture is I.1.1:
20g formula VII compound is as the 40 weight % aqueous solution:
R 15—[N(CH 2CH 2O) 6H] 2 VII，
R wherein 15Be cis-(CH 2) 8-CH=CH-(CH 2) 7CH 3
2.8g acrylic acid, 128g styrene, 245.2g n-butylacrylate,
12g N-methylol methacrylamide is dissolved in the 68g water,
12g N, N-dimethylaminopropyl Methacrylamide (" DMAPMAM "):
Figure A200780042698D00231
The dense formic acid of 172g distilled water and 5g.
Mixture is I.1.2:
2g 2, and 2 '-azo two (2-amidine propane) dihydrochloride is in the complete deionized water of 100ml
In the 5L still that anchor agitator, nitrogen tube connector and three metering devices are housed, add the emulsion that comprises the complete deionized water of 250ml, 4g formula VII compound (being dissolved in the 6ml water) and 1g formic acid.Then nitrogen was fed the gained emulsion 1/4 hour altogether.Subsequently this emulsion is heated to 75 ℃.
Then, add the 66g mixture I.1.1 with the 10g mixture I.1.2, and make this mixture begin polymerization.In case polymerization begins, then begin to add simultaneously remaining mixture I.1.1 with mixture I.1.2.I.1.1, mixture added in 2 hours, and I.1.2 mixture added in 2 hours 15 minutes.Temperature maintenance is 75 ℃ between charge period.
Stirred 30 minutes down at 75 ℃ after reinforced the finishing, smelly in order to dispel then, in 90 minutes, be metered into 1.7g simultaneously and close pyrosulfurous acid salting liquid (the 13 weight % aqueous solution) with the acetone of 30ml distilled water diluting with the t-butyl hydroperoxide solution (the 70 weight % aqueous solution) of 30ml distilled water diluting and 9.2g.
Then dispersion is cooled to room temperature.The dispersion that can so obtain filters 125 μ m nets then.Filtration lasts 4 minutes.Remove about 1g grumeleuse.
Obtain pH and be the aqueous dispersion of 3.6 (A.1).Solids content is 37.6 weight %, and dynamic viscosity is 245mPas.Particle diameter distributes: maximum 100nm.Glass transition temperature T gBe-1 ℃.
I.2 prepare particle
I.2.1 prepare particle (B.1)
Prepare following mixture:
Mixture is I.2.1:
The complete deionized water of 200g
252g styrene (42 weight %), 9g (1.5 weight %) acrylic acid, 30g (5 weight %) ALMA, 9g (1.5 weight %) N, N-dimethylaminopropyl Methacrylamide (" DMAPMAM "):
Figure A200780042698D00241
1.5g dense formic acid, 6g formula VII compound is as 40 weight %, the aqueous solution:
R 15—[N(CH 2CH 2O) 6H] 2 VII，
R wherein 15Be cis (CH 2) 8-CH=CH-(CH 2) 7CH 3
Mixture is I.2.2:
1.8g 2,2 '-azo two (2-amidine propane) dihydrochloride is in the complete deionized water of 50ml
Mixture is I.2.3:
The complete deionized water of 265g
6g formula VII compound is as the 40 weight % aqueous solution:
R 15—[N(CH 2CH 2O) 6H] 2 VII
9g (15 weight %) N-methylol methacrylamide is the 15 weight % aqueous solution,
9g (1.5 weight %) N, N-dimethylaminopropyl Methacrylamide (" DMAPMAM "),
(2.4g 0.4 weight %) acrylic acid, 96g (16 weight %) styrene, 183.4g (30.6 weight %) n-butylacrylate,
4g formic acid.
Mixture is I.2.4:
1.8g 2,2 '-azo two (2-amidine propane) dihydrochloride is in the complete deionized water of 50ml
In the 5L still that agitator, nitrogen tube connector and 3 metering devices are housed, add the suspension that I.2.1 obtains with the formula VII compound (on seeing) of the 15g40 weight % aqueous solution by the complete deionized water of mixing 300ml, 1g formic acid, 51.5g mixture.Make nitrogen by the emulsion that can so obtain 1 hour.Then this emulsion is heated to 75 ℃.I.2.2 and observe polymerization and begin add the 10ml mixture.Begin simultaneously then to add remaining mixture I.2.1 with mixture I.2.2.I.2.1, mixture added in 2 hours, and I.2.2 mixture added in 2 hours 45 minutes.Temperature maintenance is 75 ℃ in the reinforced process.Mixture further stirred 15 minutes down at 75 ℃ after I.2.2 feeding in raw material and finishing, and obtained nuclear (a.1).
Then, begin simultaneously to add mixture I.2.3 with mixture I.2.4.I.2.3, mixture added in 2 hours, and I.2.4 mixture added in 2 hours 15 minutes.Temperature maintenance is 75 ℃ in reinforced process.Obtain shell (b.1).
Stirred 15 minutes down at 75 ℃ after reinforced the finishing, smelly in order to dispel then, in 60 minutes, be metered into 2.6g simultaneously and close pyrosulfurous acid salting liquid (the 13 weight % aqueous solution) with the acetone of 30ml distilled water diluting with the t-butyl hydroperoxide solution (the 70 weight % aqueous solution) of 30ml distilled water diluting and 13.8g.
Be cooled to room temperature then.The dispersion that can so obtain filters 125 μ m nets then.Filtration lasts 4 minutes.Remove about 2g grumeleuse
Obtain pH and be 3.8 and comprise the dispersion WD.1 of particle (B.1).Solids content is 37.3 weight %, and dynamic viscosity is 65mPas.Particle diameter distributes: maximum 80nm.
I.2.2 prepare particle (B.2)
Prepare following mixture:
Mixture is I.3.1:
The complete deionized water of 192g
258.9g styrene, 2.1g acrylic acid, the 30g allyl methacrylate, 9g DMAPMAM,
1.6g formula VII compound (on seeing), the 40 weight % aqueous solution.
Mixture pH I.3.1 uses dense formic acid to be adjusted to 4.0.
Mixture is I.3.2:
0.5g 2,2 '-azo two (2-amidine propane) dihydrochloride is in the complete deionized water of 100ml
Mixture is I.3.3:
The complete deionized water of 286g,
6g formula VII compound (on seeing), the 40 weight % aqueous solution,
9g N-methylol methacrylamide, the 15 weight % aqueous solution,
9g N, N-dimethylaminopropyl Methacrylamide (" DMAPMAM "),
2.1g acrylic acid, 96g styrene, the 183.9g n-butylacrylate,
4g formic acid.
Mixture is I.34:
1.5g 2,2 '-azo two (2-amidine propane) dihydrochloride is in the complete deionized water of 100ml
The formic acid that adds the complete deionized water of 200ml and fully concentrate in the 5L still that agitator, nitrogen tube connector and 3 metering devices are housed is 4 to set pH.Make nitrogen by the solution that can so obtain 1 hour.Then this solution is heated to 75 ℃.Begin simultaneously then to add mixture I.3.1 with mixture I.3.2.I.3.1, mixture added in 2 hours, and I.3.2 mixture added in 2 hours 15 minutes.Temperature maintenance is 75 ℃ in the reinforced process.Mixture further stirred 30 minutes down at 75 ℃ after I.3.2 feeding in raw material and finishing, and obtained nuclear (a.2).
Then, begin simultaneously to add mixture I.3.3 with mixture I.3.4.I.3.3, mixture added in 2 hours, and I.3.4 mixture added in 2 hours 15 minutes.Temperature maintenance is 75 ℃ in reinforced process.Obtain shell (b.2).
Further stirred 15 minutes down after reinforced the finishing at 75 ℃, smelly in order to dispel then, in 60 minutes, be metered into 2.1g the t-butyl hydroperoxide solution (the 70 weight % aqueous solution) of 30ml distilled water diluting and the HO-CH that 1.5g uses the 30ml distilled water diluting simultaneously 2SO 2Na solution.Under 75 ℃, stirred again 30 minutes then.
Cool to room temperature then.Subsequently available dispersion is filtered 125 μ m nets.Filtration lasts 4 minutes.Remove about 2g grumeleuse.
Obtain pH and be 3.4 and comprise the dispersion WD.2 of particle (B.2).Solids content is 37.9 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: be 334nm to the maximum.
Each self-contained cationic particle of particle (B.1) and (B.2).
II. prepare preparaton of the present invention F.1～F.4 with control formulation V-F.5～V-F.7
Stir together and water is made into 1 liter and use each preparaton in stirred vessel by each component in will showing.
Table 1: the composition of preparaton of the present invention and control formulation
F.1 F.2 F.3 F.4 V-F.5 V-F.6 V-F.7
Acetate (g/l) 1 1 1 1 1 1 1
(B.1)(g/l) 15 10 - - 30 - -
(B.2)(g/l) - - 20 15 - - 30
(A.1)(g/l) 15 20 10 15 - - -
(C1.1)(g/l) 45 45 45 45 45 45 45
pH 4.7 4.5 4.5 4.6 4.7 4.9 4.5
(C1.1): M n10 weight % methacrylic acids and 90 weight %CH for 30000g/mol (GPC) 2=CHCOO-CH 2-CH 2-O-n-C 6F 13Random copolymer aqueous dispersion (20 weight % solids content)
III. textile treatment
Use following textiles:
Cotton: 1m * 30cm, 100% woven cotton, bleaching, mercerising is not handled, twill construction, basic weight 196g/m 2(" Co ").
Use following equipment in all cases:
Padder: Mathis makes, and model is HVF12085, and contact pressure is 1.6 crust.It is 81% that the setting of contact pressure should make wet pickup (based on fibre weight) in all cases.This liquid is in room temperature, except as otherwise noted.
Drying machine: from the continuous drier of Mathis THN 12589
Method of testing:
Spray test: AATCC 22-2001, oil is estimated: AATCC 118-2002,
Hydrophobization: AATCC 193-2004, smoothness: AATCC 124-2001
Wash conditions: 30 ℃ of soft circulations down, the gentle laundry detergent of 15g/l,
Rinsing maching: Miele Novotronic T440C is provided with: drum dried, manual wet ironing.
Co is padded (step 1) with aqueous fluid by table 1.Then in dry 2 minutes of 110 ℃ of following tenterings, 160 ℃ of oven dry 2 minutes down, obtain textiles Co.1～Co.4 of the present invention or contrast textiles V-Co.5～V-Co.7 then by table 2.
Table 2: the textiles of processing and performance thereof
Handle F.1 F.2 F.3 F.4 V-F.5 V-F.6 V-F.7
Textiles Co.1 Co.2 Co.3 Co.4 V-Co.5 V-Co.6 V-Co.7
The mist test 100 100 100 100 100 100 100
The property 8 8 8 8 7 5 6
Aquation 10 10 10 10 9 6 9
Mist test (behind the 10HL) 70 80 80 80 70 80 70
Par (behind the 10HL) 7 8 7 7 7 5 6
Aquation (behind the 10HL) 10 10 10 10 9 6 7
HL: above-mentioned household laundry circulation.

Claims (12)

1. aqueous formulation that comprises following component:
(A) at least a film forming addition (being total to) polymer,
(B) comprise the particle of nuclear (a) and at least one described nuclear (a) shell (b) in addition and optional
(C) at least a hydrophobizers.
2. according to the aqueous formulation of claim 1, wherein said film forming addition (being total to) polymer (A) is selected from polyacrylate and polyurethane.
3. according to the aqueous formulation of claim 1 or 2, wherein said hydrophobizers (C) is selected from polymer containing halogen (C1), alkane (C2), per molecule and has at least one C 10-C 60Compound of alkyl (C3) and polysiloxanes (C4).
4. according to each aqueous formulation among the claim 1-3, the number average diameter of wherein said particle (B) is 20-1000nm.
5. according to each aqueous formulation among the claim 1-4, the shell (b) that wherein said particle (B) comprises comprises the ester of at least a ethylenically unsaturated carboxylic acids or at least a ethylenically unsaturated carboxylic acids or the crosslinked or crosslinkable copolymer of acid amides.
6. according to each aqueous formulation among the claim 1-5, wherein said nuclear (a) or described shell (b) comprise cation copolymer.
7. at least a according to each the purposes of preparaton in coated surfaces among the claim 1-6.
8. by using at least a method according to each aqueous formulation coated surfaces among the claim 1-6.
9. method according to Claim 8 wherein makes described surface contact heat treatment then with at least a according to each aqueous formulation among the claim 1-6.
10. according to Claim 8 or 9 method, handle with priming paint (E) on wherein said surface, contacts suitable then words heat treatment according to each aqueous formulation among the claim 1-6 with at least a then.
11. coated surfaces that obtains by according to Claim 8 method.
12. a method for preparing according to each aqueous formulation among the claim 1-6 comprises following component and water are mixed together:
(A) at least a film forming addition (being total to) polymer,
(B) comprise the particle of nuclear (a) and at least one described nuclear (a) shell (b) in addition,
The optional at least a hydrophobizers of S (C) and
(D) optional at least a auxiliary agent.
CNA2007800426981A 2006-11-17 2007-11-15 Aqueous formulations and use thereof Pending CN101535560A (en)

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JP2010510395A (en) 2010-04-02
EP2092110A2 (en) 2009-08-26

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